CO2 mineralization in produced and industrial effluent water by pH-swing carbonation

ABSTRACT

Effluent water is combined with carbon dioxide sourced from a carbon dioxide-containing emission stream to produce a reaction solution. The pH of the reaction solution is controlled to induce precipitation of a carbonate salt from the reaction solution.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a National Stage Entry of International Application No. PCT/US2018/040373, filed Jun. 29, 2018, which claims the benefit of and priority to U.S. Provisional Application No. 62/527,622, filed Jun. 30, 2017, the contents of which are incorporated herein by reference in their entirety.

STATEMENT OF GOVERNMENT SUPPORT

This invention was made with government support under Grant Numbers DE-FE0029825 and DE-FE0031705, awarded by U.S. Department of Energy. The government has certain rights in the invention.

TECHNICAL FIELD

This disclosure generally relates to an aqueous carbonation route for carbon dioxide (CO₂) sequestration.

BACKGROUND

Produced effluent water from oil and gas extraction operations, industrial (aqueous) effluents containing dissolved minerals, desalination brine, sea water, and other effluent water compose large waste streams based on volume. It is desired to treat these waste streams to derive value, while employing management costs and handling practices that are both cost effective and environmentally sustainable. The treated water may also find potential uses in irrigation, rangeland restoration, and animal consumption, among others.

Produced effluent water generally represents a waste product in the petroleum industry. If an oil or gas operator is to utilize a low-cost disposal option, the treated water has to meet the specifications set by regulators. Specifications can be related to oil and grease discharge, chemical content (e.g., total dissolved solids, TDS), physical characteristics (e.g., temperature), and biological content (e.g., coliforms per liter). Extraction of salts or impurities is often the most important part of water treatment systems, as TDS in produced water can range from about 2,000 ppm to about 150,000 ppm. In addition, choices on the water treatment method depends on the water's TDS content. Oil and gas operators have attempted evaporation, distillation, membrane filtration, electric separation, and chemical treatments to remove salts. However, further improvements in the treatment in effluent water remain desired, specially to derive added-value.

It is against this background that a need arose to develop the embodiments described herein.

SUMMARY

In some embodiments, a method includes: combining effluent water with carbon dioxide sourced from a carbon dioxide-containing emission stream to produce a reaction solution; and controlling the pH of the reaction solution to induce precipitation of a carbonate salt from the reaction solution.

In some embodiments, a method includes: combining effluent water with carbon dioxide sourced from a carbon dioxide-containing emission stream to produce a reaction solution; and inducing precipitation of a carbonate salt from the reaction solution in the presence of a pH buffer agent.

Other aspects and embodiments of this disclosure are also contemplated. The foregoing summary and the following detailed description are not meant to restrict this disclosure to any particular embodiment but are merely meant to describe some embodiments of this disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

For a better understanding of the nature and objects of some embodiments of this disclosure, reference should be made to the following detailed description taken in conjunction with the accompanying drawings.

FIG. 1. Direct aqueous carbonation using produced effluent water and flue gas.

FIG. 2. Representative carbon (C), calcite (CaCO₃), and magnesite (MgCO₃) concentrations as a function of pH in an effluent water solution that is saturated with CO₂. As the pH is elevated, such as by provision of a reusable, regenerable buffer agent (base) or by adding additional effluent, the total dissolved C in solution depletes as calcite (or another carbonate salt) precipitates. This example calculation is for a closed system in which total dissolved C is depleted as calcite precipitates, and for an initial Ca concentration of about 1400 ppm. If the solution is allowed to maintain a fixed saturation with CO₂ (e.g., in a practical sense, by continually exposing the solution with CO₂) as calcite precipitates, the solubility with respect to the carbonates (e.g., MgCO₃, (Ca,Mg)CO₃ phases, and other carbonates such as BaCO₃ and SrCO₃) can increase.

DETAILED DESCRIPTION

Embodiments of this disclosure are directed to a direct aqueous carbonation route for CO₂ sequestration using calcium- and magnesium-rich solutions such as produced effluent water derived from oil and gas extraction operations, industrial mineral-containing effluent water, desalination brine, sea water, and other effluent water. In some embodiments, direct carbonation takes advantage of increased carbonation reaction rates that occur in the liquid (aqueous) phase.

FIG. 1 shows an example implementation of a direct aqueous carbonation method using produced effluent water and flue gas from a coal-fired power plant as may be especially suited to co-located coal power plant and enhanced oil recovery (EOR) sites. As shown in FIG. 1, coal is fed into a boiler 100, where combustion takes place to produce fly ash, bottom ash, and flue gas containing CO₂. The flue gas is fed into a flue gas desulfurizer 102 to remove sulfur dioxide (SO₂) and is then released into the atmosphere through a flue gas stack 104. Water extracted from the ocean or from riverine or other sources is fed into the boiler 100 and transported through conduits within the boiler 100. Heat from the combustion of coal converts the feed sea water into steam, which drives a turbine 106 connected to the boiler 100, producing electricity through a generator 108. After driving the turbine 106, the exhausted steam, which may be at least partially condensed, is converted into a liquid form using a condenser 110.

In the direct aqueous carbonation method, flue gas obtained after desulfurization is extracted and reacted with effluent water (e.g., as secured from near-shore, or on-shore hydrocarbon extraction operations) or water that may be exhausted from the turbine 106 to yield a carbonation reaction that can precipitate carbonate salts, such as in the form of relevant polymorphs of calcium carbonate and magnesium carbonate and related compounds. The gas reactant can encompass both dilute and concentrated flue gas streams with CO₂ concentrations ranging from about 1% CO₂ to near pure/substantially 100% CO₂ (v/v).

In addition to flue gas from coal-fired power plants, other CO₂-containing emission streams can be used as a CO₂ source. Thus, in addition to implementation in the context of power plants fired by coal and natural gas, CO₂ emissions from chemical and petrochemical plants, methane processing operations, and so forth, can be used.

As shown in the inset of FIG. 1, flue gas is combined with effluent water in a concentrator 112, wherein the concentrations of one or both of the reactants can be increased or otherwise adjusted, and the resulting reaction solution is fed into a carbonation reactor 114 connected to the concentrator 112. The concentrator 112 can include, for example, a capacitive concentrator (e.g., including a pair of electrodes connected to an electrical source) to increase concentrations of calcium and magnesium ions, a mixer/compressor to increase CO₂ concentration, or both. A carbonation reaction takes place within the reactor 114 to precipitate carbonate salts, such as in the form of calcium carbonate and magnesium carbonate, which can either be deposited underground or serve as a valuable product for other uses, for example, as fine and coarse mineral aggregates for use in concrete. A pH buffer agent can be fed into the reactor 114 and introduced into the reaction solution to adjust or control its pH to promote the carbonation reaction. In place of, or in combination with, the use of a pH buffer agent, pH control can be performed by mixing solute-rich (e.g., in terms of Ca and Mg) and solute-poor (e.g., in terms of Ca and Mg following depletion of these species due to the precipitation of carbonate salts) liquid streams until the desired pH level is achieved. Subsequent to the carbonation reaction, the resulting treated water, which would have reduced amount of TDS, can either be discharged into the ocean, deposited underground or be subjected to further treatment. Alternatively, or in conjunction with the method described above, the treated water can be leveraged further for other uses, such as for oil recovery operations as shown in FIG. 1, or other uses including irrigation, rangeland restoration, animal consumption, and agriculture. A controller 116 (e.g., including a processor and an associated memory storing processor-executable instructions) can be included to direct operation of various components shown in FIG. 1.

The pH of effluent water can vary between about 5.5 and about 9, although typical produced effluent water features a pH between about 6.5 and about 7.8 and is rich in dissolved calcium and magnesium. When CO₂ (from a flue gas) is injected at or near atmospheric conditions, the pH can be suppressed down to about 5.2, thereby enforcing increases in calcium (and magnesium) solubility as shown in FIG. 2. By exploiting the pH-induced solubility shift, in a pH range between about 6 and about 8, dissolved ions, such as calcium and magnesium, can be precipitated as carbonate salts.

A more acidic solution decreases the driving force for subsequent carbonate salt precipitation. Therefore, direct carbonation is enhanced in a solution that has a higher pH. To reduce the amount and cost of chemicals for promoting carbonation reactions, the pH of an acidic solution is controlled using a recyclable pH buffer agent. Examples of recyclable pH buffer agents include ammonium salts, such as ammonium bicarbonate (NH₄HCO₃). An ammonium salt can be collected by evaporation and subsequent heating to regenerate ammonia. However, this process can specify an undesirable amount of energy and produce non-environmentally friendly substances. Another example of such recyclable pH buffer agent can include heterogeneous buffer agents, such as polymer-supported phosphonic acid or other polymer-supported (basic) buffer agents which can be conveniently sourced in the form of polymer beads that offer high surface area. The use of a polymer buffer agent can be explained by an ion exchange reaction. Ion exchange of the polymer buffer agent may be described by the following reaction scheme where protons, H⁺ are removed from solution by exchanging alkaline cations with the buffer agent (where: R is a suitable functional group that is associated with one or more types of exchangeable cations including alkaline metals for basic buffering, or protons if the buffer is to maintain acidic conditions; see example of base buffer below): R−Cations(Na⁺,Ca²⁺,Mg²⁺)+HCO₃ ⁻↔R−H+Cations(Na⁺,Ca²⁺,Mg²⁺)CO₃ ⁻ Therefore, the resulting pH depends on the concentration of positively charged species in the buffer agent, and on the concentration of relevant counterions in the produced water. One possible functional group that is relevant in a reusable buffer agent is carboxylate (RCOO⁻). Advantageously, heterogeneous buffer agents are often less hazardous, solvent-free, and are environmentally friendly. Following a desired level of direct (aqueous) carbonation, the heterogeneous buffer agent, in particulate form, can be removed from a reaction solution by filtration and then reused effectively. Additional examples of heterogeneous buffer agents include clays supporting ion exchange reactions, such as zeolites including cations that can be exchanged for protons.

Advantages of some embodiments of the direct aqueous carbonation route for CO₂ sequestration include the following. Unlike CO₂ geo-sequestration, indirect carbonation, and other sequestration methods, the direct aqueous carbonation route avoids the criterion for: 1) stripping CO₂ from flue gas using a scrubbing media; 2) compression of CO₂ for long-distance transport by pipeline; and 3) large amounts of acid and base for allowing mineral dissolution and carbonation. Importantly, unlike amine stripper-based CO₂ processing, the direct carbonation route proposed herein imposes no criterion for steam generated by the power plant thereby eliminating any “parasitic” energy losses. Furthermore, by exploiting the temperature dependent solubility and precipitation kinetics of carbonate salts, waste heat derived from flue gases can be re-used to improve carbonation process efficiencies. Since carbonate solubility is both pH and temperature dependent, both of these parameters can be optimized to improve the process throughput.

The following are example embodiments of this disclosure.

In a first aspect according to some embodiments, a method includes: combining effluent water with carbon dioxide sourced from a carbon dioxide-containing emission stream to produce a reaction solution; and controlling the pH of the reaction solution to induce precipitation of a carbonate salt from the reaction solution.

In some embodiments of the first aspect, controlling the pH includes increasing the pH of the reaction solution. In some embodiments, controlling the pH includes adjusting the pH of the reaction solution to about 6 or greater, about 6.5 or greater, about 7 or greater, about 7.5 or greater, or about 8 or greater, and up to about 9 or greater.

In some embodiments of the first aspect, controlling the pH includes introducing a pH buffer agent in the reaction solution. In some embodiments, the pH buffer agent is a heterogeneous buffer agent. In some embodiments, the heterogeneous buffer agent is a polymer-supported buffer agent. In some embodiments, the heterogeneous buffer agent is a clay to support ion exchange reaction. In some embodiments, the method further includes, subsequent to the precipitation of the carbonate salt, recovering the heterogeneous buffer agent by filtration.

In some embodiments of the first aspect, the carbonate salt includes at least one of calcium carbonate or magnesium carbonate, or another carbonate (e.g., barium carbonate) or other related solids.

In some embodiments of the first aspect, the carbon dioxide-containing emission stream is a flue gas stream.

In a second aspect according to some embodiments, a method includes: combining effluent water with carbon dioxide sourced from a carbon dioxide-containing emission stream to produce a reaction solution; and inducing precipitation of a carbonate salt from the reaction solution in the presence of a pH buffer agent.

In some embodiments of the second aspect, inducing the precipitation of the carbonate salt includes controlling the pH of the reaction solution, using the pH buffer agent. In some embodiments, inducing the precipitation of the carbonate salt includes adjusting the pH of the reaction solution to about 6 or greater, about 6.5 or greater, about 7 or greater, about 7.5 or greater, or about 8 or greater, and up to about 9 or greater.

In some embodiments of the second aspect, the pH buffer agent is a heterogeneous buffer agent. In some embodiments, the heterogeneous buffer agent is a polymer-supported buffer agent. In some embodiments, the heterogeneous buffer agent is a clay to support ion exchange reaction. In some embodiments, the method further includes, subsequent to the precipitation of the carbonate salt, recovering the heterogeneous buffer agent by filtration.

In some embodiments of the second aspect, the carbonate salt includes at least one of calcium carbonate or magnesium carbonate, or another carbonate (e.g., barium carbonate) or other related solids.

In some embodiments of the second aspect, the carbon dioxide-containing emission stream is a flue gas stream.

In a third aspect according to some embodiments, an apparatus includes: a concentrator to produce a reaction solution from effluent water and carbon dioxide sourced from a carbon dioxide-containing emission stream; and a carbonation reactor connected to the concentrator to receive the reaction solution and induce precipitation of a carbonate salt from the reaction solution. In some embodiments, the carbonation reactor is configured to control the pH of the reaction solution. In some embodiments, the carbonation reactor is configured to introduce a pH buffer agent in the reaction solution.

As used herein, the singular terms “a,” “an,” and “the” may include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to an object may include multiple objects unless the context clearly dictates otherwise.

As used herein, the term “set” refers to a collection of one or more objects. Thus, for example, a set of objects can include a single object or multiple objects.

As used herein, the terms “connect,” “connected,” and “connection” refer to an operational coupling or linking. Connected objects can be directly coupled to one another or can be indirectly coupled to one another, such as via one or more other objects.

As used herein, the terms “substantially” and “about” are used to describe and account for small variations. When used in conjunction with an event or circumstance, the terms can refer to instances in which the event or circumstance occurs precisely as well as instances in which the event or circumstance occurs to a close approximation. For example, when used in conjunction with a numerical value, the terms can refer to a range of variation of less than or equal to ±10% of that numerical value, such as less than or equal to ±5%, less than or equal to ±4%, less than or equal to ±3%, less than or equal to ±2%, less than or equal to ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, or less than or equal to ±0.05%.

Additionally, concentrations, amounts, ratios, and other numerical values are sometimes presented herein in a range format. It is to be understood that such range format is used for convenience and brevity and should be understood flexibly to include numerical values explicitly specified as limits of a range, but also to include all individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly specified. For example, a range of about 1 to about 200 should be understood to include the explicitly recited limits of about 1 and about 200, but also to include individual values such as about 2, about 3, and about 4, and sub-ranges such as about 10 to about 50, about 20 to about 100, and so forth.

While the disclosure has been described with reference to the specific embodiments thereof, it should be understood by those skilled in the art that various changes may be made and equivalents may be substituted without departing from the true spirit and scope of the disclosure as defined by the appended claims. In addition, many modifications may be made to adapt a particular situation, material, composition of matter, method, operation or operations, to the objective, spirit and scope of the disclosure. All such modifications are intended to be within the scope of the claims appended hereto. In particular, while certain methods may have been described with reference to particular operations performed in a particular order, it will be understood that these operations may be combined, sub-divided, or re-ordered to form an equivalent method without departing from the teachings of the disclosure. Accordingly, unless specifically indicated herein, the order and grouping of the operations are not a limitation of the disclosure. 

What is claimed is:
 1. A method comprising: combining effluent water with carbon dioxide sourced from a carbon dioxide-containing emission stream to produce a reaction solution; and controlling the pH of the reaction solution with a regenerable heterogeneous pH buffer agent to induce precipitation of a carbonate salt from the reaction solution, wherein the regenerable heterogeneous pH buffer agent is a clay to support ion exchange reaction, or a polymer-supported buffer agent.
 2. The method of claim 1, wherein the method further comprises regenerating the regenerable heterogeneous pH buffer agent.
 3. The method of claim 1, wherein controlling the pH includes increasing the pH of the reaction solution.
 4. The method of claim 1, wherein controlling the pH includes adjusting the pH of the reaction solution to 6 or greater.
 5. The method of claim 1, wherein controlling the pH includes adjusting the pH of the reaction solution to 6.5 or greater.
 6. The method of claim 1, further comprising, subsequent to the precipitation of the carbonate salt, recovering the heterogeneous pH buffer agent by filtration.
 7. The method of claim 1, wherein the carbon dioxide-containing emission stream is a flue gas stream.
 8. A method comprising: combining effluent water with carbon dioxide sourced from a carbon dioxide-containing emission stream to produce a reaction solution; and inducing precipitation of a carbonate salt from the reaction solution in the presence of a regenerable heterogeneous pH buffer agent, wherein the regenerable heterogeneous pH buffer agent is a clay to support ion exchange reaction, or a polymer-supported buffer agent.
 9. The method of claim 8, further comprising, subsequent to the precipitation of the carbonate salt, recovering the regenerable heterogeneous pH buffer agent by filtration.
 10. The method of claim 8, wherein inducing the precipitation of the carbonate salt includes controlling the pH of the reaction solution using the regenerable heterogeneous pH buffer agent.
 11. The method of claim 8, wherein the carbon dioxide-containing emission stream is a flue gas stream. 